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Title: Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers

Abstract

Relations between molecular design, chemical functionality, and stimulus-triggered response are important for a variety of applications of polymeric systems. In this paper, reactive amphiphilic block copolymers (BCPs) of poly(2-vinylpyridine)-block-poly(2-vinyl-4,4-dimethylazlactone) (PVP-b-PVDMA) were synthesized and assembled into microgels capable of incorporating functional amines. The composition of the PVP-b-PVDMA BCPs was varied to control the number of reactive sites in the spherical aggregates created by self-assembly of PVP-b-PVDMA BCPs in a 2-propanol/THF (v:v = 19:1) solvent mixture, which is selective for PVP. PVDMA and PVP segments were selectively cross-linked by 1,4-diaminobutane (DAB) or 1,4-diiodobutane (DIB) to fabricate core- and corona-cross-linked azlactone-containing microgels, respectively. Non-cross-linked aggregates of PVP-b-PVDMA and DIB-cross-linked microgels dissociate when exposed to THF, which is a good solvent for both blocks. However, the DAB-cross-linked BCP microgels swell in THF, suggesting the formation of a stable, three-dimensional network structure. Finally, because of their ability to be reactively modified in ways that allows their stability or disassembly characteristics to be tailored, these azlactone-containing BCP microgels provide an attractive platform for applications in a wide range of fields, including catalysis, imaging, molecule separation, and guest loading for targeted delivery.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]
  1. Shandong Univ., Jinan (China). National Engineering Research Center for Colloidal Materials. School of Chemistry and Chemical Engineering; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  2. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences
  4. Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemistry. Dept. of Chemical and Biomolecular Engineering
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States); Shandong Univ., Jinan (China)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Program of Qilu Young Scholars of Shandong Univ. (China); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1468208
Grant/Contract Number:  
AC05-00OR22725; 1131252; 1512221; 21704057
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 10; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., and Kilbey, S. Michael. Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.8b00405.
Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., & Kilbey, S. Michael. Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers. United States. doi:10.1021/acs.macromol.8b00405.
Wang, Xu, Davis, Jesse L., Aden, Bethany M., Lokitz, Bradley S., and Kilbey, S. Michael. Fri . "Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers". United States. doi:10.1021/acs.macromol.8b00405. https://www.osti.gov/servlets/purl/1468208.
@article{osti_1468208,
title = {Versatile Synthesis of Amine-Reactive Microgels by Self-Assembly of Azlactone-Containing Block Copolymers},
author = {Wang, Xu and Davis, Jesse L. and Aden, Bethany M. and Lokitz, Bradley S. and Kilbey, S. Michael},
abstractNote = {Relations between molecular design, chemical functionality, and stimulus-triggered response are important for a variety of applications of polymeric systems. In this paper, reactive amphiphilic block copolymers (BCPs) of poly(2-vinylpyridine)-block-poly(2-vinyl-4,4-dimethylazlactone) (PVP-b-PVDMA) were synthesized and assembled into microgels capable of incorporating functional amines. The composition of the PVP-b-PVDMA BCPs was varied to control the number of reactive sites in the spherical aggregates created by self-assembly of PVP-b-PVDMA BCPs in a 2-propanol/THF (v:v = 19:1) solvent mixture, which is selective for PVP. PVDMA and PVP segments were selectively cross-linked by 1,4-diaminobutane (DAB) or 1,4-diiodobutane (DIB) to fabricate core- and corona-cross-linked azlactone-containing microgels, respectively. Non-cross-linked aggregates of PVP-b-PVDMA and DIB-cross-linked microgels dissociate when exposed to THF, which is a good solvent for both blocks. However, the DAB-cross-linked BCP microgels swell in THF, suggesting the formation of a stable, three-dimensional network structure. Finally, because of their ability to be reactively modified in ways that allows their stability or disassembly characteristics to be tailored, these azlactone-containing BCP microgels provide an attractive platform for applications in a wide range of fields, including catalysis, imaging, molecule separation, and guest loading for targeted delivery.},
doi = {10.1021/acs.macromol.8b00405},
journal = {Macromolecules},
number = 10,
volume = 51,
place = {United States},
year = {2018},
month = {5}
}

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